NG HA HC

Chemical Kinetics

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NG HA HC
ng ha hc tm hiu xem phn ng xy ra
nhanh chm ra sao
C 4 yu t quan trng nh hng ln vn tc:
Nng tc cht
nhit
hat ca xc tc
tnh cht b mt.
Mc ch: Tm hiu cc phn ng ha hc
mc phn t nhm m hnh ho cc qu
trnh trong t nhin.
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Vn tc phn ng
Reaction Rates
Vn tc ca mt phn ng c o bng bin
thin ca nng theo thi gian.
Xem phn ng
A B
(nng ca tc
cht A)
Vntc =
---------------------------------- (thi gian)
y l biu thc ca vn tc trung bnh
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Chemical Kinetics
Reaction Rates

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Vn tc trung bnh
Ti t = 0 (time zero): 1.00 mol A (100 red
spheres); 0.0 mol B
Ti t = 20 min: 0.54 mol A, 0.46 mol B.
Ti t = 40 min: 0.30 mol A, 0.70 mol B.
Vy:

moles of B
Vtb
t

moles of B at t 10 moles of B at t 0

10 min - 0 min
0.26 mol - 0 mol

0.026 mol/min
10 min - 0 min

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Chemical Kinetics
Reaction Rates

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Rates
Termsbnh
of Concentrations
Vn
tcintrung

C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

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Vn tc tc thi (instantaneous
rate)
Phn ng chm dn theo thi gian (the
average rate decreases with time).
Dng ng tip tuyn ca ng cong
biu din vn tc theo thi gian. D
dc ca tip tuyncho ta vn tc tc
thi (instantaneous rate) ca phn ng
ti thi im
Du ca vn tc ph thuc h s gc ca
ng tip tuyn
T nay khi ni ti vn tc l ni ti vn
tc tc thi
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Vn tc tc thi (instantaneous
rate)
Rates in Terms of Concentrations

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Chemical Kinetics
Reaction Rates and Stoichiometry
For the reaction
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)
we know

C4 H 9Cl C4 H 9OH
Rate

t
t

In general for
aA + bB cC + dD
1 A
1 B 1 C 1 D
Rate

a t
b t
c t
d t
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Biu thc vn tc phn ng

Vi nhng nng u khc nhau, ngi
ta nhn thy rng vn tc phn ng tng
khi nng tng:
NH4+(aq) + NO2-(aq) N2(g) + 2H2O(l)

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Biu thc vn tc phn ng

NH4+(aq) + NO2-(aq) N2(g) + 2H2O(l)

Khi nng [NH4+] tng 2 ln, nng

[NO2-] khng i th vn tc phn ng tng
2 ln
Khi nng [NO2-] tng 2 ln, nng
[NH4+] khng i th vn tc phn ng
cng tng 2 ln
vn tc [NH4+][NO2-].
Biu thc vn tc phn ng
vn tc = k[NH4+][ NO2-].
k l hng s tc ca phn ng
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Bc ca phn ng
Mt biu thc vn tc c dng

vn tc = k[reactant 1]m[reactant 2]n

Bc phn ng c nh ngha l tng s m
ca cc nng
Phn ng trn c gi l c bc m theo
reactant 1, bc n theo reactant 2 v bc tng
cng l m+n
Biu thc vn tc l mt c trng c xc
nh t thc nghim ca mt phn ng; N
khng th c tnh ton da trn h s t
lng ca phng trnh ho hc.
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S bin i ca vn tc theo nng

Dng vn tc u xc nh biu thc vn tc
Mt phn ng c bc zero theo mt tc cht nu
thay i nng tc cht khng nh hng ln
vn tc.
Mt phn ng l bc nht nu tng gp i nng
vn tc tng gp i.
Mt phn ng l bc hai nu tng gp i nng
vn tc tng 22 ln.
Mt phn ng l bc n nu tng gp i nng
vn tc tng 2n ln.
Lu : hng s vn tc khng ph thuc bc phn
ng
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The Change of Concentration with Time

Phn ng bc nht n gin
Ta c th chuyn biu thc vn tc thnh phng
trnh biu din nng theo thi gian.
i vi phn ng bc nht, vn tc tng gp i khi
nng tng gp i.

ln A t kt ln A 0
ng ln[A]t theo t l mt ng thng vi dc
-k v tung gc ln[A]0.
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Phn ng bc nht n gin

ln A t kt ln A 0

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Bn sinh phn ng (Half-Life) t1/2

Half-life t1/2 l thi gian nng tc cht gim cn mt
na so vi ban u.
Tc l half life, t1/2 , l thi gian nng tc cht A gim
t [A]0 xung [A]0.
Biu thc ca t1/2

t1
2

ln 1
k

2 0.693

half life, t1/2 , khng ph thuc nng u ca tc cht [A]o

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Bn sinh phn ng (Half-Life) t1/2

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The Change of Concentration with Time

Phn ng bc hai n gin
Cho phn ng bc hai vi ch mt tc cht A

1
1
kt
A t
A 0
ng biu din 1/[A]t theo t l mt ng
thng vi dc k v tung gc 1/[A]0
ng biu din ca ln[A]t theo t khng phi l
ng thng.

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Phn ng bc hai n gin

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Bn sinh phn ng (Half-Life) t1/2

Bn sinh phn ng (Half-Life) t1/2 ph thuc nng
u ca tc cht [A]o

1
t1
2 k A 0
Mt phn ng c biu thc vn tc dng:
rate = k[A][B],
l phn ng c bc chung l bc hai nhng bc
nht theo A v B.
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S bin i ca vn tc theo nhit

Hu ht cc phn ng u xy ra nhanh hn khi
tng nhit . (VD. thc phm b h khi khng
c tr lnh.)
Do trong biu thc vn tc khng cha i lng
c trng cho nhit , i lng ny phi c
cha trong k.
Nhit tng lm vn tc phn ng tng do k tng.

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nhit v vn tc

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nhit v vn tc
Xt phn ng bc nht:
CH3NC CH3CN.
Khi nhit tng t 190 C ln 250 C, hng s
vn tc tng t 2.52 10-5 s-1 ln 3.16 10-3 s-1.
Ti sao nh hng ca nhit li ln nh
vy?

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Thuyt va chm (The Collision Model)

T nhng quan st cho thy vn tc phn ng
ph thuc vo nng v nhit , ngi ta
a ra l thuyt nhm gii thch nhng kt qu
quan st ny.
The collision model:
phn ng xy ra, cc phn t phi va chm
mnh vi nhau
S ln va chm cng nhiu, vn tc phn ng
cng ln

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The Collision Model

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The Collision Model

S phn t hin din cng nhiu, kh nng va
chm cng ln, vn tc cng ln.
Nhit cng cao, cc phn t cng s hu
nhiu nng lng, vn tc cng ln.
Lu : Khng phi mi va chm u dn n
phn ng. Thc s ch mt phn nh s va
chm dn n s to thnh sn phm.
phn ng xy ra, cc phn t phi va chm
ng hng vi nng lng ln mi to
thnh sn phm.
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Nng lng hat ha (Activation Energy)

Theo Arrhenius: Cc phn t phi s hu mt
nng lng ti thiu no th phn ng mi
xy ra. Ti sao? V:
to thnh sn phm, phi c qu trnh t
ni xy ra tc cht.
Qu trnh t ni cn nng lng
Nng lng hat ha Ea l nng lng ti thiu
khi mo mt phn ng ha hc.

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Activation Energy

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Activation Energy
Xem qu trnh sp xp ni ca acetonitrile:
H3C N C

H3C

N
C

H3C C N

Trong H3C-NC, ni C-NC bin dng cho n khi ni

C-N b gy v phn NC gn ngc li vo phn H3C.
Dng cu trc ny gi l phc cht hat ng (activated
complex) hay trng thi chuyn tip (transition state).
Nng lng cn thit lm bin dng v b gy ni
trn chnh l nng lng hat ha (activation energy)
Ea.
Khi ni C-N b gy, phn NC c kh nng tip tc xoay
to nn ni mi C-CN.
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Activation Energy

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Activation Energy
S thay i nng lng ca phn ng l s chnh lch
nng lng gia CH3NC v CH3CN.
Nng lng hot haThe activation energy is the
difference in energy between reactants, CH3NC and
transition state.
The rate depends on Ea.
Notice that if a forward reaction is exothermic (CH3NC
CH3CN), then the reverse reaction is endothermic (CH3CN
CH3NC).

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Temperature and Rate

Activation Energy
Consider the reaction between Cl and NOCl:
If the Cl collides with the Cl of NOCl then the products are
Cl2 and NO.
If the Cl collided with the O of NOCl then no products are
formed.

We need to quantify this effect.

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Temperature and Rate

Activation Energy

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Temperature and Rate

The Arrhenius Equation
Arrhenius discovered most reaction-rate data obeyed the Arrhenius
equation:

k Ae

Ea

RT

k is the rate constant, Ea is the activation energy, R is the gas constant (8.314
J/K-mol) and T is the temperature in K.
A is called the frequency factor.
A is a measure of the probability of a favorable collision.
Both A and Ea are specific to a given reaction.

If we have a lot of data, we can determine Ea and A graphically by

rearranging the Arrhenius equation:
If we do not have a lot of data, then we can use

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Temperature and Rate

The Arrhenius Equation
If we have a lot of data, we can determine Ea and A
graphically by rearranging the Arrhenius equation:

Ea
ln k
ln A
RT
If we do not have a lot of data, then we can use

k1 Ea 1 1
ln

k2
R T2 T1

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Reaction Mechanisms
The balanced chemical equation provides information
about the beginning and end of reaction.
The reaction mechanism gives the path of the
reaction.
Mechanisms provide a very detailed picture of which
bonds are broken and formed during the course of a
reaction.

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Reaction Mechanisms
Elementary Steps
Elementary step: any process that occurs in a single
step.
Molecularity: the number of molecules present in an
elementary step.
Unimolecular: one molecule in the elementary step,
Bimolecular: two molecules in the elementary step, and
Termolecular: three molecules in the elementary step.

It is not common to see termolecular processes

(statistically improbable).

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Reaction Mechanisms
Elementary Steps
Elementary steps must add to give the balanced
chemical equation.
Intermediate: a species which appears in an
elementary step which is not a reactant or product.

Rate Laws of Elementary Steps

The rate law of an elementary step is determined by
its molecularity:
Unimolecular processes are first order,
Bimolecular processes are second order, and
Termolecular processes are third order.

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Reaction Mechanisms
Rate Laws of Multistep Mechanisms
Rate-determining step: is the slowest of the
elementary steps.
Therefore, the rate-determining step governs the
overall rate law for the reaction.

Mechanisms with an Initial Fast Step

It is possible for an intermediate to be a reactant.
Consider
2NO(g) + Br2(g) 2NOBr(g)

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Reaction Mechanisms
Mechanisms with an Initial Fast Step
2NO(g) + Br2(g) 2NOBr(g)
The experimentally determined rate law is
Rate = k[NO]2[Br2]
Consider the following mechanism
k1
NOBr2(g)
Step 1: NO(g) + Br2(g)
k-1

Step 2: NOBr2(g) + NO(g)

k2

(fast)

2NOBr(g) (slow)

for which the rate law is (based on Step 2):

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Reaction Mechanisms
Mechanisms with an Initial Fast Step
The rate law is (based on Step 2):
Rate = k2[NOBr2][NO]
The rate law should not depend on the concentration
of an intermediate because intermediates are usually
unstable.
Assume NOBr2 is unstable, so we express the
concentration of NOBr2 in terms of NOBr and Br2
assuming there is an equilibrium in step 1 we have

k1
NOBr2 [NO][Br2 ]
k1
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Reaction Mechanisms
Mechanisms with an Initial Fast Step
By definition of equilibrium:
k1[NO][Br2] = k-1[NOBr2]
Therefore, the overall rate law becomes

k1
Rate k 2
[NO]2 [Br2 ]
k 1

Note the final rate law is consistent with the

experimentally observed rate law.

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Catalysis
A catalyst changes the rate of a chemical reaction.
There are two types of catalyst:
homogeneous, and
heterogeneous.

Chlorine atoms are catalysts for the destruction of

ozone.

Homogeneous Catalysis
The catalyst and reaction is in one phase.
Hydrogen peroxide decomposes very slowly:
2H2O2(aq) 2H2O(l) + O2(g).
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Catalysis
Homogeneous Catalysis
2H2O2(aq) 2H2O(l) + O2(g).
In the presence of the bromide ion, the decomposition
occurs rapidly:
2Br-(aq) + H2O2(aq) + 2H+(aq) Br2(aq) + 2H2O(l).
Br2(aq) is brown.
Br2(aq) + H2O2(aq) 2Br-(aq) + 2H+(aq) + O2(g).
Br- is a catalyst because it can be recovered at the end of the
reaction.

Generally, catalysts operate by lowering the activation

energy for a reaction.
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Catalysis
Homogeneous Catalysis

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Catalysis
Homogeneous Catalysis
Catalysts can operate by increasing the number of
effective collisions.
That is, from the Arrhenius equation: catalysts
increase k be increasing A or decreasing Ea.
A catalyst may add intermediates to the reaction.
Example: In the presence of Br-, Br2(aq) is generated
as an intermediate in the decomposition of H2O2.
When a catalyst adds an intermediate, the activation
energies for both steps must be lower than the
activation energy for the uncatalyzed reaction.
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Catalysis
Heterogeneous Catalysis
The catalyst is in a different phase than the reactants
and products.
Typical example: solid catalyst, gaseous reactants and
products (catalytic converters in cars).
Most industrial catalysts are heterogeneous.
First step is adsorption (the binding of reactant
molecules to the catalyst surface).
Adsorbed species (atoms or ions) are very reactive.
Molecules are adsorbed onto active sites (red spheres)
on the catalyst surface.
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Catalysis
Heterogeneous Catalysis

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Catalysis
Heterogeneous Catalysis
Consider the hydrogenation of ethylene:
C2H4(g) + H2(g) C2H6(g), H = -136 kJ/mol.
The reaction is slow in the absence of a catalyst.
In the presence of a metal catalyst (Ni, Pt or Pd) the
reaction occurs quickly at room temperature.
First the ethylene and hydrogen molecules are adsorbed
onto active sites on the metal surface.
The H-H bond breaks and the H atoms migrate about the
metal surface.

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Catalysis
Heterogeneous Catalysis
Consider the hydrogenation of ethylene:
C2H4(g) + H2(g) C2H6(g), H = -136 kJ/mol.
When an H atom collides with an ethylene molecule on the
surface, the C-C bond breaks and a C-H bond forms.
When C2H6 forms it desorbs from the surface.
When ethylene and hydrogen are adsorbed onto a surface,
less energy is required to break the bonds and the activation
energy for the reaction is lowered.

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Catalysis
Enzymes
Enzymes are biological catalysts.
Most enzymes are protein molecules with large
molecular masses (10,000 to 106 amu).
Enzymes have very specific shapes.
Most enzymes catalyze very specific reactions.
Substrates undergo reaction at the active site of an
enzyme.
A substrate locks into an enzyme and a fast reaction
occurs.
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Catalysis
Enzymes

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Catalysis
Enzymes
The products then move away from the enzyme.
Only substrates that fit into the enzyme lock can be
involved in the reaction.
If a molecule binds tightly to an enzyme so that
another substrate cannot displace it, then the active
site is blocked and the catalyst is inhibited (enzyme
inhibitors).
The number of events (turnover number) catalyzed is
large for enzymes (103 - 107 per second).

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Catalysis
Nitrogen Fixation and Nitrogenase
Nitrogen gas cannot be used in the soil for plants or
animals.
Nitrogen compounds, NO3, NO2-, and NO3- are used in
the soil.
The conversion between N2 and NH3 is a process with
a high activation energy (the NN triple bond needs to
be broken).
An enzyme, nitrogenase, in bacteria which live in root
nodules of legumes, clover and alfalfa, catalyses the
reduction of nitrogen to ammonia.
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Catalysis
Nitrogen Fixation and Nitrogenase

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Catalysis
Nitrogen Fixation and Nitrogenase
The fixed nitrogen (NO3, NO2-, and NO3-) is consumed
by plants and then eaten by animals.
Animal waste and dead plants are attacked by
bacteria that break down the fixed nitrogen and
produce N2 gas for the atmosphere.

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Chemical Kinetics

End of Chapter 14
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